|||||||

USOO.5551960A
United States Patent (19) 11 Patent Number: 5,551,960
Christianson 45) Date of Patent: Sep. 3, 1996
54 ARTICLE FOR POLISHINGSTONE 4,652,275 3/1987 Bloecher et al. ......................... 511298
4,675,975 6/1987 Kucharczyk et al. . 29/566
75) Inventor: Todd J. Christianson, Oakdale, Minn. 4,735,632 4/1988 OZman et al. ............................ 51/295
73) Assignee: Minnesota Mining and (List continued on next page.)
Manufacturing Company, St. Paul, FOREIGN PATENT DOCUMENTS
Minn. 478427 9/1966 Belgium.
21) Appl. No.: 441,426 (List continued on next page.)
(22 Filed: May 15, 1995 OTHER PUBLICATIONS
Related U.S. Application Data 3M Product Literature No.: 60-4400-2429-1 (112.5) JR,
“3M Flexible Diamond Discs' (1990).
a a of Ser. No. 436,891, May 8, 1995, abandoned,
62) Division Coated Abrasives-Modern Tool of Industry,s 1st Ed.
which is a continuation of Ser. No. 30,787, Mar 12, 1993, McGraw-Hill Book Company, Inc., (1958) pp. 333-334.
abandoned, R. B. Seymour & C. E. Carraher, Jr., Polymer Chemistry,
5 2nd Ed (1988).
: s a sins, 5.5; Cowie, J. M. G., “Polymers: Chemistry and Physics of
(52) Yor s Modern Materials' (1973).
58) Field of Search ............................... 51/295, 297, 298
Primary Examiner-Deborah Jones
56) References Cited Attorney, Agent, or Firm-Gary L. Griswold; Walter N.
Kirn; Doreen S. L. Gwin
U.S. PATENT DOCUMENTS
57 ABSTRACT
2,115,897 5/1938 Wooddell et al. ...................... 451/529
2,907,146 10/1959 Dyar ................ . . 51/195 In accordance with the present invention, a method of
3,048,482
3,098,329
8/1962 Hurst....
7/1963 Doran ..............
. . 51298 polishing stone and an article for use in the method are
3,401,491 3/1965 Schnabel et al.
SA presented in which the stone has at least one exposed
3,468,079 9/1969 Kaufman ......... IgE surface, the method comprising the steps of
3,517,466 6/1970 Bouvier ... ... 51358 a) bringing into frictional contact an abrasive article to the
3,605.349 9/1971 Anthon ...................................... 51402 exposed surface of the stone; and
3,770,400 11/1973 Hallewell .................................. 5i/295 b) refining the exposed surface of the stone with the
4,047,903 9/1977 Hesse et al. ... 51/298 abrasive article, preferably in the presence of water,
4,088,729 5/1978 Sherman ..... . . 264/259 wherein the abrasive article comprises a plurality of
4,098,329 7/1978 Culver ......... ... 1651140 abrasive particles adhered to a backing (preferably a
4,106,915 8, 1978 Kagawa et al. ............................. 51A96
4,1666 9/1978 Kalbow ........... ... 51/295 flexible backing) by a binder (preferably a resilient
4,255.164 3/1981. Butzkeet al. ... 51/295 binder), wherein the binder comprises a cured resin
4,311,489 1/1982 Kressner ......... ... 51/298 derived from a resin comprising unsaturated addition
4,317,660 3/1982 Kramis et al. .. ... 51/295 polymerizable units. The binder and abrasive particles
4,355,489 10/1982 Heyer et al. ... 51f400 (and plasticizer when used) form a resilient composite
4,457,766 7/1984 Caul ........ 51/298 having a hardness no greater than 20 HK but at least 1
4,547,204 10/1985 Caul ........ ... 51298 HK. Use of the articles and method of the invention
4,588,419 5/1986 Caul et al. ... 51295 efficiently increases the gloss of stone surfaces.
4,617,767 10/1986 Ali .......... ... 511358
4,642,126 2/1987 Zador et al. ........ ............... 51/295
4,652,274 3/1987 Boettcher et al. ........................ 51/298 28 Claims, 3 Drawing Sheets

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U.S. PATENT DOCUMENTS 5,107,626 4/1992 Mucci ................................... 51/281R

4,750.95 6/1988 Tomita et all 51/298 5,152,917 10/1992 Pieper et al. .............................. 51/295
f al/Ws OIIllia C al. .......... . . . . . . . . . . . . . 5,174,795 12/1992 Wiand ............... ... 51/295
4,751,138 6/1988 Tumey et al................... ... 428/323 5,178,646 1/1993 Barber, Jr. et al. 51/299
4,754,580 7/1988 Mattson ......... ... 51/177 5,213,588 5/1993 Wong et al. ... ... 51/298
4,773,920. 971988 Chasman et al. .. ... 51/295 5,216,846 6/1993 Takahashi ................................. 51/326
4,799,939 1/1989 Bloecher et al. .. ... 51/293 5,274.959 1/1994 D al 51/103 R
4,836,832 6/1989 Tumey et al. ... 51/293 sal f is yer et al. ............................
4,898,598 2/1990 Zapata ......... ... 511309
4,903,440 2/1990 Larson et al. ... ... 51/298 FOREIGN PATENT DOCUMENTS
4,930,266 6/1990 Calhoun et al. ... ... 51/293
4,945,687 8/1990 Scheider et al. ... ... 511394 0004454 10/1979 European Pat. Off..
4,974,373 12/1990 Kawashima et al. ... 51/295 0345239 12/1989 European Pat. Off..
5,011,512 4/1991 Wald et al. ........ ... 51/295 0434378A1 6/1991 European Pat. Off..
5,011,513 4/1991 Zador et al. .... ... 51/295 52-74990 6/1977 Japan.
5,014,468 5/1991 Ravipati et al. ... 51/295 2043501 10/1980 United Kingdom.
5,015,266 5/1991 Yamamoto . ... 51/293 2057484 4/1981 United Kingdom.
5,092.90 3/1992 deKoketal.".5i/295 2094824 9/1982 United Kingdom.
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 5,551,960
1.
ARTICLE FOR POLISHING STONE
This is a division of application Ser. No. 08/436,891,
filed May 8, 1995, which is a continuation of Ser. No.
08/030,787, filed Mar. 12, 1993, now abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention pertains to a method of polishing stone
with an abrasive article. The abrasive article comprises a
backing having a plurality of abrasive particles bonded to
the backing by means of a resilient binder comprising an
addition polymerized resin.
2. Related Art
Stone materials, like marble and granite, are widely used
in buildings, monuments, homes, offices and the like. Stone
materials can be synthetically made or quarried from natural
deposits in the earth. In some instances it is desirable to have
a very smooth or high gloss finish on the exposed surface of
the stone. In order to achieve this high gloss, the stone is
typically subjected to several steps. First, the stone is
quarried or mined. Then it is cut to the desired length or
dimensions, for instance by an abrasive coated wire saw. If
the stone material needs to be further dimensioned, or if a
contoured surface is desired, it can be dimensioned with
bonded abrasives (abrasive particles and binder molded into
a hardened mass). In this step, there may be several types
and grades of bonded abrasives which are utilized. Addi
tionally, surface defects in the stone surface can be removed
with abrasive products comprising abrasive particles bonded
together in a metal binder, referred to as "metal bonded
abrasives,' such as those known under the trade designation
3M Flexible Metal Bond "Diamond Abrasives', Grades
M250, M125, M74, M40 and M20, commercially available
from Minnesota Mining and Manufacturing Company, St.
Paul, Minn. ("3M"). Finally, the stone is polished with an
abrasive article to a desired surface finish or "gloss.” Gloss
relates to the surface shininess or luster and involves the
ability of the surface to reflect light. The polishing step will
generally remove any remaining defects and scratches pro
duced by earlier abrading steps. In the polishing step there
may be used a series of abrasive articles with sequentially
finer grades. An example of such a product is that known
under the trade designation "3M Flexible Resin Bond Dia
mond Abrasives', Grades R30, R10 and R2, commercially
available from 3M.
To achieve a high gloss, the average scratch depth needs
to be substantially reduced. If scratch depth is not reduced,
light may not be specularly reflected, resulting in a lower
gloss. What is desired in the abrasive industry is an efficient
method to provide a high gloss on a stone surface.
SUMMARY OF THE INVENTION
In accordance with the present invention, a method of
refining stone in which the stone has at least one exposed
surface is presented, the method comprising the steps of:
a) bringing into frictional contact an abrasive article to the
exposed surface of the stone; and
b) refining the exposed surface of the stone with the
abrasive article, preferably in the presence of water,
wherein the abrasive article comprises a plurality of
abrasive particles adhered to a backing (preferably a
flexible backing) by a binder, the abrasive particles and
cured resin forming a resilient abrasive composite,
2
wherein the binder comprises a cured resin derived
from a resin comprising a plurality of unsaturated
addition polymerizable units. As used herein the term
"units' includes monomers and oligomers. The term
“refining” when referring to the method of the inven
tion includes polishing (i.e., increasing gloss), but also
includes methods in which gloss is not substantially
improved but average scratch depth in the surface is
reduced.
10 A preferred method of refining stone is one in which the
stone having at least one exposed surface is polished, the
method comprising the steps of:
a) bringing into frictional contact an abrasive article to the
exposed surface of the stone, and
15 b) polishing the exposed surface of the stone with the
abrasive article in the presence of water, wherein the
abrasive article comprises a plurality of abrasive par
ticles adhered to a flexible backing by a binder, the
abrasive particles and binder forming a resilient abra
20 sive composite, wherein the binder comprises a resin
having polymerized units, the polymerized units having
been polymerized by a free radical mechanism.
Another aspect of the invention is drawn toward the
abrasive article useful in the method of the invention, the
25 abrasive article comprising abrasive particles adhered to a
backing by a binder, the abrasive particles and binder
forming a resilient abrasive composite, the binder compris
ing a cured resin derived from a resin comprising a plurality
of unsaturated addition polymerizable units and an effective
30 amount of a plasticizer, with the abrasive particles present in
the composite in an amount ranging from about 1 to about
25 (more preferably ranging from about 3 to about 15)
weight percent of the weight of the composite. As used
herein the term "effective amount' of a plasticizer means
35 that the plasticizer is present in the composite in an amount
sufficient to lower the glass transition temperature of the
cured resin, preferably by at least 10° C. This effectively
makes the composite more resilient during abrading.
One preferred abrasive article comprises a woven poly
40 ester backing having first and second major surfaces which
is sealed on at least one of its major surfaces with a
thermoplastic resin presize coating, preferably athermoplas
tic polyester resin. Discrete nodules of abrasive composite
are adhered to the presize resin.
45 As used herein a "resin comprising a plurality of unsat
urated addition polymerizable units' polymerizes via a free
radical or ionic mechanism at sites of monomer unsaturation
(i.e. at-C=C-sites). During the curing or polymerization
process, free radicals or ions are generated by exposing the
50 resin (or resin plus initiator, when necessary) to an energy
source such as ultraviolet radiation, visible radiation, an
electron beam, and the like. Another useful energy source is
thermal energy. Resins which are useful in forming abrasive
articles useful in the invention preferably include monomers
55 selected from acrylates, acrylamides, and vinyl compounds.
One preferred binder is derived from a combination of an
oligomeric acrylated urethane resin, a monomeric acrylated
urethane resin, a plasticizer, and a suspending agent, the
latter useful as a rheology modifier during coating of the
60 binder precursor onto the backing.
Binders useful in the invention are preferably formed
from a binder precursor composition which comprises an
unsaturated addition polymerizable "resin' and may com
prise optional ingredients. As used herein"resin' is a general
65 term denoting monomers, oligomers, and combinations
thereof.) After the unsaturated addition polymerizable resin
is "cured' (i.e., polymerized), the cured mass is then termed
 5,551,960
3 4
a "binder." Thus it is important to ensure that optional
ingredients do not substantially interfere with the curing
process, or render the composite hardness outside of the
desired range.
The term "refine” means that the average scratch depth of
the original stone surface is reduced and/or gloss is
increased, measured using standard equipment. one way to
measure depth of scratch is with a profilometer that traces
the surface of the stone. The refining step will polish the
stone surface such that the average scratch depth is reduced,
thereby generating a higher gloss.
The term “flexible' when referring to the preferred back
ing denotes that the abrasive article is able to conform to
surface irregularities in the stone, such as corners, seams,
engraved lettering, and the like. The term "resilient' when
used in reference to the composite means that the composite
is capable of deforming along with the backing, and is
capable of efficiently polishing stone surfaces to increase the
gloss. To meet these preferred properties, it has been dis
covered that the composite preferably has an average Knoop
hardness ("HK') of no more than 15 HK (kg/mm) for
refining marble, but at least 1 HK, the HK measured using
a 100 gram load. Note that the maximum Knoop hardness
may be as high as 20 HK depending on the stone surface. For
example, it may be necessary to employ composites having
hardness of about 20 HK when refining granite. When the
maximum value of 15 HK is used herein this designates
marble as the stone. In contrast, cured phenolic resins
exhibit hardness values of about 50 HK.
Prior to refining the stone, the stone surface typically has
defects or coarse scratches remaining from the physical
modification process. During refining, these defects or
coarse scratches are reduced in depth or removed and a
higher gloss surface is generated. There may be more than
one abrasive article used in the refining step, i.e., there may
be used a series abrasive articles that employ abrasive
particles of different grades. The refining step typically and
preferably starts with an abrasive article that has larger
average abrasive particle size and progresses through a
series of abrasive articles having average abrasive particle
size lower than the preceding article. During the refining
step, the gloss of the stone surface is increased, preferably to
a high gloss (i.e. greater than 60 glossmeter value at 60°
incidence angle).
The abrasive articles of the invention unexpectedly are
more durable (i.e., have a longer useful life) when used for
polishing a variety of stone surfaces.
Further understanding of the invention will become
apparent from the following.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a plan view of one preferred abrasive article in
accordance with the invention;
FIG. 2 is an enlarged cross section taken along the line
2-2 of the abrasive article illustrated in FIG. 1;
FIG. 3 is an enlarged sectional view of a second abrasive
article embodiment in accordance with the invention;
FIG. 4 is an enlarged sectional view of a third abrasive
article embodiment in accordance with the invention;
FIG. 5 is a plan view of a fourth abrasive article embodi
ment in accordance with the invention;
FIG. 6 is a plan view of a fifth abrasive article embodi
ment in accordance with the invention;
FIG. 7 is an enlarged sectional view of another abrasive
article embodiment in accordance with the invention; and
FIG. 8 is a plan view of another preferred abrasive article
in accordance with the invention.
DESCRIPTION OF PREFERRED
5
EMBODIMENTS
This invention pertains to a method of refining (preferably
polishing) stone with an abrasive article that comprises a
plurality of abrasive particles that are bonded to a backing by
10 means of a binder comprising a cured resin derived from a
resin comprising a plurality of unsaturated addition poly
merizable units.
The term "stone' of course, is a broad term, and herein
includes igneous, sedimentary, metamorphic or hybrid rock.
15
Examples of stone types which may benefit from the method
of this invention include granites, limestones (including
marble), shale (including slate), sandstones (including
quartz) and basalts. Granites are igneous rocks comprised
primarily of alkali feldspar, quartz and plagioclase.
20
The end use of the stone may be in a home or a
commercial environment. The stone may be used for deco
rative purposes or structural purposes. Examples of decora
tive and/or structural uses include paneling, headstones,
monuments, wainscoting, floor tiles (including terrazzo),
25
Stair treads, columns, spindles, table tops, fireplace manties,
counter tops, walls, vaults, walkways, patios, sills, floors,
steps and the like.
The stone will have at least one surface that is to be
30 polished. The dimensions of the stone can vary, from very
small to very large. For instance, the dimension can be from
about 0.1 millimeters (such a marble grains in terrazzo) to
over tens of meters. Typically, the stone dimensions will
range from about 0.1 millimeters to 5 meters. As previously
35 noted, the stone surface may be relatively flat or it may have
some contour associated with it. These contours can be in the
shape of curves or corners.
Abrasive Articles Useful in Refining Stone
A. Binders
40 The binder functions to adhere (sometimes referred to
herein as “bond') the abrasive particles to each other and to
the backing. The hardness of the binder, and thus the
hardness of the composite of binder and abrasive particles,
is critical to the performance of the inventive abrasive article
45 during refining of the stone surface. Preferred binders are
those which result in the composite hardness being less than
15 HK (for polishing marble), more preferably ranging from
about 3 to about 9, but in all cases at least about 1 HK.
Composites having hardness within these ranges result in an
50 abrasive article that very efficiently refines stone surfaces
and generate high gloss on those surfaces. If the composite
hardness is too high, then the resulting abrasive article will
actually be too efficient and not refine the stone surface, or
will not increase gloss. (As used herein "efficient' when
55 referring to abrasion means a high level of stone removal per
unit time and a correspondingly low loss of abrasive article,
in the same unit of time. The former is typically referred to
as 'cut' while the latter is referred to as "wear'.)
Knoop hardness determinations were performed essen
60 tially using the method described in American Society for
Testing Materials ("ASTM") C-849, which is incorporated
herein by reference. Knoop hardness has units of kg/mm’
herein.
"Resins comprising a plurality of unsaturated addition
65 polymerizable units' includes resins in which polymeriza
tion is initiated and propagated by either free radicals or ions
(including anions or cations), and the terms "polymerizable'
 5,551,960
5 6
and "polymerized" are meant to include both chain growth
and crosslinking reactions. In the present invention, poly
merization is initiated by exposing the binderprecursor to an
energy source (in the presence of an initiator if necessary)
such as thermal energy or radiation energy. Examples of
suitable radiation energy include particle radiation such as
electron beam irradiation and the like, and nonparticle
radiation such as, ultraviolet radiation and visible light.
Examples of resins which cure by a free radical mecha
nism and which are useful in the invention include acrylated 10
urethanes, acrylated epoxies, acrylated polyesters, ethyleni
cally unsaturated compounds, aminoplast derivatives having
pendant unsaturated carbonyl groups, isocyanurate deriva
tives having at least one pendant acrylate group, isocyanate
derivatives having at least one pendant acrylate group and 15
mixtures and combinations thereof. The term "acrylated' is
meant to include monoacrylated, monomethacrylated, multi
acrylated, and multi-methacrylated monomers, oligomers
and polymers.
Preferred acrylated urethanes are diacrylate esters of 20
hydroxy-terminated and diisocyanate-extended polyesters
or polyethers. The average molecular weight of preferred
acrylated urethane oligomer resins ranges from about 300 to
about 10,000, more preferably from about 400 to about
7,000. Examples of commercially available acrylated ure 25
thanes of this type include those known under the trade
designations “Uvithane” 782, “Uvithane" 783, "Uvithane"
788, and “Uvithane' 893 Specialties, Louisville, Ky.).
Examples of preferred acrylated epoxies are diacrylate
esters of epoxy resins, such as the diacrylate esters of 30
bisphenol A epoxy resin. Examples of commercially avail
able acrylated epoxies include those known under the trade
designations "CMD 3500”, “CMD 3600”, and “CMD 3700”
(available from Radcure Specialties) and "CN103”,
“CN104”, “CN111”, “CN112' and “CN114” (available from 35
Sartomer Company).
Examples of preferred polyester acrylates include those
known under the trade designations "Photomer' 5007 and
"Photomer' 5018 (available from Henkel Corporation).
“Ethylenically unsaturated resins' include both mono 40
meric and polymeric compounds that contain atoms of
carbon, hydrogen and oxygen, and optionally, nitrogen and
the halogens. Oxygen or nitrogen atoms or both are gener
ally present in ether, ester, urethane, amide, and urea groups.
Ethylenically unsaturated resins for use in producing abra 45
sive articles useful in the invention preferably have a
molecular weight of less than about 4,000 and are preferably
esters made from the reaction of compounds containing
aliphatic monohydroxy groups or aliphatic polyhydroxy
groups and unsaturated carboxylic acids, such as acrylic 50
acid, methacrylic acid, itaconic acid, crotonic acid, isocro
tonic acid, maleic acid, and the like. Representative
examples of acrylate resins include isobornyl acrylates,
methyl methacrylate, ethyl methacrylate styrene, divinyl
benzene, vinyl toluene, ethylene glycol diacrylate, ethylene 55
glycol methacrylate, hexanediol diacrylate, triethylene gly
col diacrylate, trimethylolpropane triacrylate, glycerol tria
crylate, pentaerythritol triacrylate, pentaerythritol methacry
late, pentaerythritol tetraacrylate and pentaerythritol
tetraacrylate. Other ethylenically unsaturated resins include 60
monoallyl, polyallyl, and polymethallyl esters and amides of
carboxylic acids, such as diallyl phthalate, diallyl adipate,
and N,N'-diallyladipamide. Still other nitrogen containing
compounds include tris(2-acryloyloxyethyl)isocyanurate,
1,3,5-tri(2-methyacryloxyethyl)-s-triazine, acrylamide, 65
methylacrylamide, N-methylacrylamide, N,N-dimethy
lacrylamide, N-vinylpyrrolidone, and N-vinylpiperidone.
Aminoplast resins have at least one pendant alpha, beta
unsaturated carbonyl group per molecule or oligomer. These
unsaturated carbonyl groups can be acrylate, methacrylate or
acrylamide type groups. Examples of such materials include
N-hydroxymethyl-acrylamide, N,N'-oxydimethylenebi
sacrylamide, ortho and para acrylamidomethylated phenol,
acrylamidomethylated phenolic novolac and combinations
thereof. These materials are further described in U.S. Pat.
No. 4,903,440 and U.S. Ser. No. 07/659,752 (filed Feb. 24,
1991) both incorporated herein by reference.
Isocyanurate derivatives having at least one pendant acry
late group and isocyanate derivatives having at least one
pendant acrylate group are further described in U.S. Pat. No.
4,652,274, incorporated herein by reference. One preferred
isocyanurate material is a triacrylate of tris(hydroxyethyl)
isocyanurate.
It is to be understood that mixtures of the above unsat
urated addition polymerizable resins could also be
employed.
Some of the free radical curable resins are considered
oligomers, while others are considered monomers. Oligo
mers, as defined in R. B. Seymour & C. E. Carraher, Jr.,
Polymer Chemistry, 2nd Ed., are very low molecular weight
polymers in which the number of repeating units (n) equals
2 to 10. Monomers generally only consist of one unit that
does not repeat.
Depending upon how the unsaturated addition polymer
izable resin is cured or polymerized, the binder precursor
may further comprise a curing agent, (which is also known
as a catalyst or initiator). When the curing agent is exposed
to the appropriate energy source, it will generate a free
radical or ion that will initiate the polymerization process.
Examples of curing agents that when exposed to thermal
energy generate a free radical include peroxides, e.g., ben
zoyl peroxide, azo compounds, benzophenones, and quino
nes. Examples of curing agents that when exposed to ultra
violet light generate a free radical include but are not limited
to those selected from the group consisting of organic
peroxides, azo compounds, quinones, benzophenones,
nitroso compounds, acryl halides, hydrozones, mercapto
compounds, pyrylium compounds, triacrylimidazoles,
bisimidazoles, chloroalkytriazines, benzoin ethers, benzil
ketals, thioxanthones, and acetophenone derivatives, and
mixtures thereof. Examples of curing agents that when
exposed to visible radiation generate a free radical can be
found in U.S. Pat. No. 4,735,632, incorporated herein by
reference.
The binder precursor composition may further comprise a
plasticizer which functions to reduce the glass transition
temperature of the cured resin, thus rendering the composite
more flexible (able to deform with the backing) and resilient
(able to deform due to abrasion of a surface). The plasticizer
should be compatible with the unsaturated addition poly
merizable resin and other optional resins and ingredients
such that there is little or no phase separation. Examples of
useful plasticizers for use in the invention include polyvinyl
chloride, cellulose esters, phthalate, adipate and sebacate
esters, polyols, polyols derivatives, tricresyl phosphate, cas
tor oil and the like. The preferred plasticizers are polyol
derivatives such as polyethyleneglycol having average
molecular weight ranging from about 200 to about 1000,
more preferably about 600. The amount of plasticizer is
generally less than 30 weight percent, typically less than
about 15 weight percent and preferably less than 10 weight
percent of the total binder precursor weight.
In addition to the unsaturated addition polymerizable
resin, the binder precursor may further comprise from about
 5,551,960
7 8
5 to about 10 weight percent of an ionically initiated epoxy
resin, preferably cationically initiated. Epoxy resins have an
oxirane and are polymerized by the ring opening. Useful
epoxy resins include monomeric epoxy resins and polymeric
epoxy resins. Examples of some preferred epoxy resins
include 2,2-bis(4-(2,3-epoxypropoxy)-phenylpropane) (dig
lycidyl ether of bisphenol) and commercially available
materials under the trade designation "Epon 828", "Epon
1004" and "Epon 1001F available from Shell Chemical
Co., “DER-331', 'DER-332' and “DER-334’ available
from Dow Chemical Company. Other suitable epoxy resins
include cycloaliphatic epoxies such as epoxy resins avail
able from Union Carbide, Danbury CT, under the trade
designation "ERL-4221', glycidyl ethers of phenol formal
dehyde novolac (e.g., "DEN-431' and “DEN-428" available
from Dow Chemical Company). Particularly preferred are
blends of unsaturated addition polymerizable resins with
other addition polymerizable resins such as those described
in U.S. Pat. No. 4,751,138 (Tumey et al.), incorporated by
reference herein.
Binder precursors useful in this invention may further
comprise optional additives which do not render the hard
ness of the resulting composite outside of the range of about
1 to about 15 HK (when marble is being polished). For
example, fillers (including grinding aids), fibers, lubricants,
wetting agents, antistatic agents, surfactants, pigments, dyes,
and suspending agents may be used. The amounts of these
materials are selected to provide an abrasive composite
having the desired hardness so that the article generates high
gloss on the stone surface being polished.
Diluents may also be used in the binder precursors. As
used herein the term "diluent' denotes a low molecular
weight (less than 500) organic material that may or may not
decrease the viscosity of the binder precursor to which they
are added. Diluents may be reactive with the resin or inert.
Low molecular weight acrylates are one preferred type of
reactive diluent. Acrylate reactive diluents preferred for use
in the invention typically have a molecular weight ranging
from about 100 to about 500, and include isobornyl acrylate,
ethylene glycol diacrylate, ethylene glycol dimethacrylate,
hexanediol diacrylate, triethylene glycol diacrylate, trim
ethylolpropane triacrylate, glycerol triacrylate, pentaeryth
ritol triacrylate, pentaerythritol trimethacrylate, pentaeryth
ritol tetraacrylate and pentaerythritol tetramethacrylate.
Methyl methacrylate and ethyl methacrylate may also be
used.
Other useful reactive diluents include monoallyl, polyal
lyl, and polymethallyl esters and amides of carboxylic acids
(such as diallyl phthalate, diallyl adipate, and N,N-diallyla
dipamide); tris(2-acryloyloxyethyl)isocyanurate, 1,3,5-tri(2- 50
methacryloxyethyl)-s-triazine, acrylamide, methylacryla
mide, N-methylacrylamide, N,N-dimethylacrylamide,
N-vinylpyrrolidone, and N-vinylpiperidone.
The binder precursor may further comprise a coupling
agent. Coupling agents may function to increase the bond 55
strength between various binder components. Examples of
coupling agents suitable for use in this invention include
organosilanes, zircoaluminates and titanates. The coupling
agent may be added directly to the binder precursor; alter
natively, the abrasive particles or filler may be first coated 60
with the coupling agent and then added to the binder
precursor.
In some cases it may be preferable to add a suspending
agent to the binder precursor composition to prevent the
particulate materials such as abrasive particles from settling 65
out of the binder precursor. Suspending agents may also
improve or maintain the desired the rheological properties of
the binder precursor. Examples of suspending agents useful
in the invention are amorphous silica fillers such as that
known under the trade description "R-972 Aerosil' com
mercially available from DeGussa Inc, New York, N.Y., and
amorphous silica fillers such as that known under the trade
designation "OX-50' also commercially available from
DeGussa Inc., which is an amorphous silica having average
particle size of 40 millimicrometers and surface area of 50
mi/g.
10 Binder precursor compositions which are slurries com
prising abrasive particles, an unsaturated addition polymer
izable resin, and optional ingredients preferably comprise by
weight between 60 to 99.9%, preferably between 75 to 99%,
more preferably between 85 to 97% resin, and between 0.01
15 to 40%, preferably between 1 to 25%, more preferably
between 3 to 15% abrasive particles. This amount of abra
sive particles has been found to provide the desired degree
of abrasion to increase the gloss of many stone surfaces.
Particularly preferred binder precursor slurries comprise
20 an oligomeric free radical curable resin, a monomeric free
radical curable resin, a plasticizer, abrasive particles and
optionally a coupling agent and a suspending agent. In these
particularly preferred slurries the slurry comprises by weight
between about 15 to 90%, preferably between 25 to 70%
25 oligomeric free radical curable resin, between about 1 to
50%, preferably between 5 to 30% monomeric free radical
curable resin, from 0 to 30%, preferably between 1 to 20%
plasticizer, from 0 to 20%, preferably between 0.5 to 10%
suspending agent and a small weight percentage of a cou
30 pling agent. The selection of the amount and type of these
materials, as mentioned previously, in the binder precursor
slurry preferably results in a binder that has sufficient
integrity to be useful as a binder for abrasive particles, but
which yields a composite having has a hardness in the
35 desired range.
It may be preferred in some instances to form the abrasive
article by use of make and size coatings. In these abrasive
article embodiments, a make coating is applied to a backing,
the abrasive particles are applied to the backing, the make
coating is exposed to conditions to at least partially cure the
make coating, and a size coating is applied over the abrasive
particles and make coating. The structure is then subjected
to conditions sufficient to cure the make and size coatings.
Optional presize and supersize coatings may also be applied
45 as known in the art.
B. Backing Materials
Backings serve the function of providing a support for the
abrasive composite formed by the combination of binder and
abrasive particles. Backings useful in the invention must be
capable of adhering to the binder after exposure of binder
precursor to curing conditions, and are preferably flexible
after said exposure so that the articles used in the inventive
method may conform to surface irregularities in the stone.
Examples of typical backings include polymeric film,
primed polymeric film, cloth, paper, vulcanized fiber, open
mesh fabrics, wovens and nonwovens and combinations
thereof. A particularly preferred backing is a woven poly
ester backing.
The backing may be treated with a thermosetting or
thermoplastic resin to reinforce the backing, protect the
fibers in the backing, seal the backing, and/or improve the
adhesion of the binder to the backing. Examples of typical
and preferred thermosetting resins include phenolic resins,
aminoplast resins, urethane resins, epoxy resins, ethyleni
cally unsaturated resins, acrylated isocyanurate resins, urea
formaldehyde resins, isocyanurate resins, acrylated urethane
resins, acrylated epoxy resins, bismaleimide resins and
 5,551,960
9 10
mixtures thereof. Examples of preferred thermoplastic resins
include polyamide resins (e.g. nylon), polyester resins and
polyurethane resins (including polyurethaneurea resins).
One preferred thermoplastic resin is a polyurethane derived
from the reaction product of a polyester polyol and an
isocyanate.
C. Abrasive Particles
Abrasive particles useful in the invention preferably have
an average particle size ranging from about 0.1 micrometer
(small particles) to 300 micrometers (large particles), usu
ally between about 1 micrometer to 30 micrometers. It is
preferred that the abrasive particles have a Mohs hardness of
at least 8, more preferably at least 9. Examples of abrasive
particles suitable for use in the invention include fused
aluminum oxide, ceramic aluminum oxide, heated treated
aluminum oxide, silicon carbide, alumina Zirconia, iron
oxide, diamond (natural and synthetic), ceria, cubic boron
nitride, garnet and combinations thereof. The term "abrasive
particles' is meant to include single abrasive particles
bonded together by a binder to form an abrasive agglomer
ate. Abrasive agglomerates are further described in U.S. Pat.
Nos. 4,311,489; 4,652,275 and 4,799,939, incorporated
herein by reference. The abrasive particle may further com
prise a surface treatment or coating, such as a coupling agent
or ceramic coating.
D. Preferred Embodiments
Referring now to the drawing figures, one preferred
embodiment of an abrasive article in accordance with the
invention is illustrated in FIGS. 1 and 2 in plan and enlarged
sectional views, respectively. A plurality of such articles are
typically and preferably attached via hook and loop fasteners
(not shown) to conventional floor maintenance machines.
Article 1 has a woven polyesterbacking 2 which is sealed on
one major surface with a thermoplastic polyester presize
coating 3. To the hardened presize coating 3 a slurry is
applied through a screen (not shown), the slurry comprising
abrasive particles and unsaturated addition polymerizable
resin to form a plurality of raised nodules 6 of composite on
the presize coating 3. The nodules of composite may vary in
shape and size, and may be distributed randomly or uni
formly on the presize coating, according to the desires of the
user. Preferably, nodules 6 are appear circular from a plan
view, all nodules having the same diameter. Nodules 6
preferably have height ranging from about 1 mm to about 30
mm. The spacing between nodules 6 and the height and
diameter of the nodules may vary from nodule to nodule
within a single article and may vary from article to article,
but are selected to optimize the increase in gloss on the stone
surface being refined. Preferably between 10 to 90%, gen
erally between 20 to 70% of the surface area of the backing
will be covered with the nodules. In some embodiments,
such as that illustrated in FIG. 8 (discussed below), it may
be desired that the composite cover up to 95 percent of the
surface of the article. During polishing, the areas free from
the composite allow for the stone swarf to be removed from
the abrading interface.
Referring now to FIG.3, another abrasive article embodi
ment 10 is illustrated in cross section, commonly referred to
as a lapping abrasive article. Articles of this type comprise
a backing 11 (preferably a woven polyester) and an abrasive
composite 12 which preferably completely covers one major
surface of backing 11. Abrasive composite 12 comprises a
plurality of abrasive particles 13 and a binder 14, preferably
a plasticized acrylic binder.
To make a lapping coated abrasive as illustrated in FIG.
3, an unsaturated addition polymerizable resin, abrasive
particles, and optional ingredients are mixed together to
form a slurry. The slurry is then coated onto the backing via
roll coating, spray coating, or the like. After the resin in the
binder precursor is cured, the slurry becomes an abrasive
composite.
Referring to FIG. 4, a cross section of an abrasive article
20 is illustrated, commonly referred to as a coated abrasive,
comprising a backing 21 having a first binder 22, commonly
referred to as a make coating, present over the front surface
23 of the backing 21. Into the make coating 22 are embedded
10 a plurality of abrasive particles 24. Over the abrasive par
ticles 24 and make coating 22 is coated a second binder 25,
commonly referred to as a size coating, which reinforces the
abrasive particles.
Referring to FIG. 5, a plan view of a lapping abrasive
15 article 30 is illustrated, the article being in the form of a
continuous belt. The article has a dot-like pattern of abrasive
composites 32 and areas free of the abrasive composite 31.
The areas free of the abrasive composite typically expose the
backing, or a presize coated onto the backing. It is within the
20 scope of this invention that the dots could be squares,
triangles, diamonds, polygons, octagons or any other geo
metric shape. As with the embodiment illustrated in FIGS. 1
and 2, preferably between 10 to 90%, generally between 20
to 70% of the surface area of the backing will be covered
25 with the abrasive composites.
Referring to FIG. 6, anotherlapping abrasive article 40 in
the form of a continuous belt is illustrated in plan view
having two continuous longitudinal rows of abrasive com
posite 42 and areas of the backing 41 free of the abrasive
30 composite. It is within the scope of this invention that the
rows could be straight, sinusoidal, parallel, or non-parallel.
Preferably between 10 to 90%, generally between 20 to 70%
of the surface area of the backing will be covered with the
abrasive composites. As with the embodiment illustrated in
35 FIG. 5, a presize coating, rather than the backing, may be
exposed.
Referring to FIG. 7, a lapping abrasive article 50 is
illustrated in cross section comprising a plurality of pyra
mids of equal height butted up against one another (i.e.,
40 preferably no backing is exposed, although this is not a
requirement). It will be apparent that the pyramids could
vary in height on a single abrasive article. The pyramids are
comprised of abrasive particles and binder, and may be
formed using the methods described in Pieper, U.S. Pat. No.
45 5,152,917, incorporated by reference herein.
Referring now to FIG. 8, illustrated in plan view is
another abrasive article embodiment 60. The abrasive com
posite in this embodiment is present on one major surface of
a backing (not shown) as a plurality of discrete areas 62
50 separated by channels 64 and 65. Channels 64 and 65 allow
water or other fluid fed through hole 66 to wash away swarf
during a stone refining process. It should be apparent that
discrete areas of abrasive composite 62 may take any of a
number of shapes. The particular pattern illustrated in FIG.
55 8, when used on discs having diameter of about 10 cm
attached to a hand-held rotary tool, has been determined to
produce high gloss stone surfaces when used in the presence
of a water flood. For a 10 cm diameter disc, channels 64 and
65 are typically about 0.25 cm wide and about the depth,
60 with the optimal width and depth easily determined by the
skilled artisan once a stone surface, down force, binder,
backing material, and abrasive particles have been selected.
A preferred abrasive article such as that illustrated in FIG. 8
has a woven polyester backing, sealed with a polyester
65 presize coating, over which is coated via a screen or other
means a binder precursor slurry as above described for the
embodiment illustrated in FIG. 1.
 5,551,960
11
Methods of Polishing Stone
Prior to polishing in accordance with the method of the
invention, the stone will typically be subjected to a variety
of physical processes (including abrading) to achieve the
desired dimensions of the stone. These previous processes
may leave scratches or expose defects in the stone surface
which typically result in a dull appearing surface. This
invention pertains to a method of polishing the stone surface
to remove enough of the scratch depth and defects to result
in a stone surface having a high gloss value. "Gloss' pertains
to the stone surface shininess or luster. When light is shone
on a stone surface, the light will be refracted or scattered by
the scratches in the surface. If the scratches are substantially
removed, or if the depth of scratch is substantially low, then
the light will be reflected, thus resulting in a high gloss
surface.
There is typically more than one "polishing' or "refining"
article used in the refining step of the method of the
invention. In general, one abrasive article having a given
average abrasive particle size is not sufficient to generate a
very high gloss surface. Rather a sequence of abrasive
articles is employed during which the average scratch depth
is continually reduced. The first abrasive article employed
will typically contain abrasive particles that have larger
particle size. As the polishing continues, the abrasive par
ticle size in the abrasive article employed is continually
reduced by the user by changing the abrasive article. This
results in a gradual reduction in scratch depth. The number
of abrasive articles, time for polishing, types of abrasive
particles and sizes of abrasive particles will depend upon
various factors such as the stone surface being polished, the
scratches and/or defects present in the stone prior to polish
ing and the desired level of gloss.
It is preferred to polish the stone in the presence of a
liquid. The liquid has several advantages associated with it.
It inhibits heat build up during polishing and removes the
swarf away from the polishing interface. "Swarf is the term
used to describe the actual stone debris that is abraded away
by the abrasive article. In some instances, the stone swarf
can damage the surface of the stone being polished. Thus it
is desirable to remove the swarf from the interface. Polishing
in the presence of a liquid also results in a finer finish on the
stone surface. This liquid can be water, an organic lubricant,
a detergent, a coolant or combinations thereof. The liquid
may further contain additives to enhance polishing. Water is
generally the preferred liquid.
During polishing the abrasive article moves relative to the
stone surface and is forced downward onto the stone surface
preferably the force ranging from about 0.35 to about 7.0
glimm, more preferably between about 0.7 to about 3.5
g/mm. If too high of a down force is used, then the abrasive
article may not refine the scratch depth and in some
instances may increase the scratch depth. Also, the abrasive
article may wear excessively if the down force is too high.
If too low down force is used, the abrasive article may not
effectively refine the scratch depth and generate the desired
level of gloss.
As stated, the stone or the abrasive article or both will
move relative to the other during the refining step. This
movement can be rotary motion, a random motion, or linear
motion. Rotary motion can be generated by attaching an
abrasive disc to a rotary tool. The stone surface and abrasive
article may rotate in the same direction or opposite direc
tions, but if in the same direction, at different rotational
speeds. For hand-held tools the tool operating rpm may
range up to 4000 rpm, while typical floor machines may
operate anywhere from about 50 to 1000 rpm depending on
12
the abrasive article employed. For example, when three
discs such as illustrated in FIGS. 1 and 2 are attached to a
conventional floor maintenance machine, each disc being
about 20 cm in diameter and equally spaced apart from each
other, the machine may have a rotational speed of about 800
rpm. Lapping machines typically operate at 25 to 500 rpm.
A random orbital motion can be generated by a random
orbital tool, and linear motion can be generated by a
continuous abrasive belt. The relative movement between
10 stone and abrasive article may also depend on the dimen
sions of the stone. If the stone is relatively large, it may be
preferred to move the abrasive article during polishing while
the stone is held stationary.
Methods of Making Abrasive Articles
15 The following procedure describes a preferred method of
making alapping abrasive article useful in the method of the
invention in which there is not a pattern associated with the
abrasive composite. First, a slurry is prepared by mixing
together abrasive particles, an unsaturated addition polymer
20 izable resin, and optional ingredients. Any conventional
technique can be employed to mix these materials. Prefer
ably, the abrasive particles should be uniformly distributed
in the binder precursor. After the slurry is prepared, it is
applied to one side of a backing by any conventional means
25 such spray coating, roll coating, die coating or knife coating.
Next, the slurry is exposed to an energy source to cure or
polymerize the unsaturated addition polymerizable resin,
and other optional resins in the slurry. In some instances it
is preferred to polymerize the resins in an inert atmosphere
30 to prevent oxygen inhibition of the addition polymerizable
resin, if it is free radically initiated free radicals.
The energy source can be heat, radiation energy or com
bination of energy sources. Examples of radiation energy
include electron beam, ultraviolet light or visible light. For
35 thermal energy, temperatures will typically and preferably
range from about 50° C. to about 250° C. for exposure times
ranging from about 15 minutes to about 16 hours. The choice
in curing conditions will depend primarily on the resin
chemistry and backing type and thickness selected. Electron
40 beam radiation, which is also known as ionizing radiation,
can be used at an energy level of about 0.1 to about 10 Mirad,
preferably at an energy level of about 1 to about 10 Mrad.
Ultraviolet radiation refers to non-particulate radiation hav
ing a wavelength ranging from about 200 to about 400
45 nanometers, preferably ranging from about 250 to 400
nanometers. Visible radiation refers to non-particulate radia
tion having a wavelength ranging from about 400 to about
800 nanometers, preferably in the ranging from about 400 to
about 550 nanometers. The time the slurry is exposed to the
50 ultraviolet or visible light can range from about 1 to 500
seconds depending on the resin type and thickness and
intensity of the radiation. For higher radiation intensities,
shorter exposure times will be required, assuming the same
binders, backing, and the like.
55 There are several methods to make a lapping abrasive
article that is patterned. Examples of useful methods are
disclosed in U.S. Pat. Nos. 3,605,349; 4,773,920; 4,930,266;
5,014,468; 5,015,266; 5,092,910. A preferred method is to
force the slurry though a screen (corresponding to the
desired pattern) and onto to the backing. The slurry is then
exposed to an energy source to polymerize the resins in the
slurry.
A method of making a patterned lapping abrasive such as
that illustrated in cross section in FIG. 7 is described in U.S.
65 Pat. No. 5,152,917 incorporated by reference herein.
One useful procedure for making a coated abrasive article
such as that illustrated in FIG. 4 useful in the method of the
 5,551,960
13
invention is now described. A make coating precursor is
applied to the front side of the backing by any conventional
technique such as spray coating, roll coating, die coating,
powder coating, hot melt coating or knife coating. The
abrasive particles are projected into the make coating pre
cursor either by drop coating or electrostatic coating. The
make coating is at least partially cured by exposing the make
coating to an energy source, Such as those energy Sources
described above. Then a size coating precursor is applied
over the abrasive particles by any conventional technique.
The size coating precursor and optionally the make coating
precursor are fully cured by exposing them to an energy
source. The resulting coated abrasive may be, and preferably
is, flexed prior to use. "Flexing' of abrasive articles, in
particular coated abrasive articles, is a term of art in the
abrasives industry which means the coated abrasive sheet is
passed over a 90 degree bend to uniformly crack the binder,
In order to manufacture a coated abrasive such as that
illustrated in the plan views of FIGS. 5 and 6 having a
pattern, the make coating can be applied to the backing in a
pattern. For instance the make coating can be applied
through a stencil or rotogravure coating. Alternatively, the
make coating may be applied to fully cover the backing and
the abrasive particles applied in a pattern. For instance, the
abrasive particles may be coated through a screen or stencil.
The following Test Methods and non-limiting Examples
will further illustrate the invention. All parts, percentages,
ratios, and the like, in the Examples are by weight unless
otherwise indicated.
Test Methods
Gloss Measurements
The following general procedure was used to measure the
gloss of the marble test specimen. The marble was first dried
to remove any residual water or swarf. The glossmeter used
was known under the trade designation "Micro-Tri-Gloss'
Catalog No. 4525 commercially available from BYK Gard
ner Inc. of Silverspring, Md. The 20° and 60° glossmeter
geometry gloss measurements were made after abrading
with the articles described in the Examples. The gloss value
was an average of four readings.
Test method ASTM D-523 was followed for determining
specular gloss values. Note that "60 glossmeter geometry
gloss' value (i.e., incident light reflected from the test
surface at incident angle measured 60 from vertical) related
to the "shininess' of the surface and correlates to the
appearance of the floor about 3 meters in front of the
observer. A "20 glossmeter geometry gloss' value relates to
the depth of the reflection and correlates to the appearance
of the floor about 60 cm in front of the observer. A reading
off a glossmeter is an indexed value, with a value of "100"
given to the glossmeter reading (from any angle) from a
highly polished, plane, black glass with a refractive index of
1.567 for the sodium D line. The incident beam is supplied
by the tester itself. A value of 0 is no or very low gloss, while
“high gloss' at 60° incidence angle geometry is about 60 or
greater (or 30 or greater at 20° incidence angle geometry),
which are preferred.
Marble Polishing Test Procedure I
The following test procedure simulated marble polishing.
There were two parts to the test machine. The base unit was
a polisher known under the trade designation "Ecomet 4"
Variable Speed Grinder-Polisher commercially available
from Buehler Ltd., Lake Bluff, Ill., which had a circular,
horizontal base plate which could be rotated at various
speeds. Located horizontally over the base unit was a head
14
unit which held six abrasive discs, each 3.8 cm in diameter,
by hook and loop fasteners, the backing of the abrasive disc
serving as the loop fastener. The head unit included a
rotational power drive known under the trade designation
5 “Automet 2' Power Head, also commercially available from
Buehler Ltd. A 28 cm diameter Cream Marfi marble disc
that was about 1 cm in thickness was adhered to the flat
horizontal circular plate of the base unit by a cured epoxy
adhesive. During polishing, the head unit containing the
10 abrasive discs was brought into contact with the marble disc
to be tested. The head unit and circular plate of the base unit
rotated in a counter motion relative to one another during
polishing. The marble disc rotated about 500 rpm, while the
head unit rotated at about 30 rpm. The polishing was done
15 wet, with water directed to the center of the marble disc. The
polishing time was 30 seconds and the down force applied
by the head unit onto the marble disc was about 7 kg during
contact by the abrasive discs. After the 30 second polishing
time, the head unit was raised and the marble disc was wiped
20 clean with a paper towel. Then four gloss measurements
were recorded.
Prior to polishing with the refining discs, the marble was
roughened for 30 seconds with flexible metal bond diamond
abrasive discs known under the trade designation "M40'
25 commercially available from 3M, for 30 seconds.
Marble Polishing Test Procedure II
This test simulated a marble floor polishing operation.
Four different marble ties were tested: Verde Jade Dark
hereinafter referred to as "green marble'; White Carrera
30 hereinafter referred to as "white marble'; Perlato hereinafter
referred to as “beige marble' and Negro Marquina herein
after referred to as "black marble'. The marble tiles were
30.5 cm by 30.5 cm square and bonded to an aluminum
plate. Twelve square abrasive articles (5 cmX5 cm) were
35 adhered to the rotatable portion of a floor polishing machine
known under the trade designation "CIMEX' by means of
hook and loop attachment systems as mentioned in Marble
Polishing Procedure I. The polishing was done under a water
flood. The down force exerted on the marble tile by the
40 machine and abrasive articles was about 33 kg.
Prior to polishing, the marble tiles were abraded sequen
tially with the following flexible metal bond diamond abra
sive grades available from 3M: “M250”, “M125”, “M74”
and "M40”, in which the number designates the grade of
45 abrasive particles in the abrasive article. The abrading
endpoint for each product was when an even surface had
occurred by visual inspection. Prior to polishing with the
methods and articles of the invention these metal bonded
abrasive articles produced the following gloss listed in Table
1.
50
TABLE 1.
GLOSS VALUES
Marble type 200 60°
55
green 0.2 1.7
white 1.0 3.3
beige 0.9 3.8
black 0.2 1.7
60
These gloss values were the base line values for the
Examples which follow.
Materials Description
65 UAR is an acrylated urethane resin commercially avail
able from Morton Thiokol of Trenton, N.J., under the
trade designation "Uvithane'893;
 5,551,960
15 16
AER is an acrylated epoxy resin commercially available
from Radcure Specialties, Inc., of Louisville, Ky., TABLE 2
under the trade designation "Ebercryl' 3500; 30 SECOND GLOSS WALUES
PAR is a polyester acrylate resin commercially available FOR EXAMPLE1
from Henkel Corp., Gulph Mills, Pa., under the trade Marble type 20o 60°
designation “Photomer' 5007;
ER is a epoxy resin commercially available from Union green 14.7 400
Carbide, Danbury Conn., under the trade designation white 44.9 70.6
“ERL-4221'; beige 13.3 35.2
black 34.0 59.4
PETA is a pentaerythritol tri- and tetra-acrylate commer 10
cially available from Sartomer of Exton, Pa;
IBA is isobornylacrylate commercially available from It can be seen that polishing for only 30 seconds on the
Sartomer Company; 30.5 cm marble square with the abrasive article of the
HDODA is 1,6-hexanedioldiacrylate commercially avail invention dramatically improved the resulting gloss com
15 pared with the base line gloss values of Table 1.
able from Sartomer Company;
PEG is polyethylene glycol (molecular weight 600) com Next, the same marble tiles from Table 2 were polished
mercially available from Union Carbide of Danbury, for an additional 30 seconds and the gloss values remea
Conn., under the trade designation "Carbowax'; sured. These gloss values can be found in Table 3.
PH1 is a photoinitiator 2-benzyl-2-N,N-dimethylamino 20
1-(4-morpholinophenyl-1-butanone) commercially TABLE 3
available from Ciba Geigy Corporation under the trade 60SECOND GEOSS VALUES
designation "Irgacure" 369; FOR EXAMPLE 1.
PH2 is a photoinitiator, cyclopentadienyl iron (II) Xylene Marble type 20° 60°
antimony hexafluoride; 25
ASF is an amorphous silica filler commercially available green 5.8 42.2
from DeGussa Inc. of New York, N.Y. under the trade white 46.9 740
designation "R972'; beige 30.8 57.5
black 317 59.8
CAl is a amino silane coupling agent (gamma-methacry
loxypropyltrimethoxy silane) commercially available 30
from Union Carbide Corporation of Danbury, Conn., The abrasive article of Example 2 was tested according to
under the trade designation "A-174'; Test Procedure II for 30 seconds on 30.5 cm marble squares
I33 is a wetting agent commercially available from Inter and the resulting gloss was measured. These gloss values
stab Chemicals, new Brunswick, N.J., under the trade can be found in Table 4.
designation "Interwet' 33; and 35
WAO is white fused aluminum oxide TABLE 4
30 SECOND GLOSS WALUES
EXAMPLES 1 AND 2 FOR EXAMPLE 2
Examples 1 and 2 were made according to the following Marble type 200 60°
procedure. The backing for these examples was a woven 40
cotton/polyester fabric that contained a thermoplastic poly green 33.4 56.4
urethane presize known under the trade designation "K2 white 93.0 100.4
Adhesive', and available from Unitherm, Inc., Cincinnati, beige 68.3 83.2
black 65.8 82.8
Ohio. This particular polyurethane presize is derived from
the reaction product of a polyester polyol and a diisocyanate, 45
although this is not known to be critical to the invention. A It can be seen that polishing for only 30 seconds on the
slurry was prepared by thoroughly mixing abrasive particles 30.5 cm marble square with the abrasive article of the
and addition polymerizable resin. The resulting slurry was invention dramatically improved the resulting gloss when
forced by spatula through a stainless steel screen that had compared with the gloss values listed in Table 3.
circular openings that were approximately 2 mm in diameter 50 Next, the same marble tiles from Table 4 were polished
onto the backing. The resulting material was exposed to one for an additional 30 seconds on the 30.5 cm marble square
Fusion Systems visible light which operated at 120 Watts/cm and the gloss values measured. These gloss values can be
with an exposure of about 3 meters/minute. This exposure found in Table 5.
initiated the polymerization of the addition polymerizable
resin to form a lapping abrasive article. 55 TABLE 5
For Example 1, the slurry consisted of 62.2 parts UAR, 60SECOND GLOSS WALUES
4.2 parts PETA, 8.4 parts IBA, 8.4 parts PEG, 0.84 part PH1, FOR EXAMPLE 2
0.1 part carbon black pigment, 10 parts synthetic diamond
that had average particle size of 15 micrometers, 4.7 parts of Marble type 200 60°
ASF and 1.2 part CAl. For Example 2, the slurry consisted 60
of 52.9 parts UAR, 20.7 parts HDODA, 8.3 parts IBA, 0.83 green 42.5 63.9
part PH1, 0.2 part iron oxide pigment, 10 parts synthetic white
beige
92.8
79.5
100.8
92.4
diamond that had average particle size of 3 micrometers, 6.0 black T6.3 90.8
parts of ASF and 1.2 part CA1.
The abrasive article of Example 1 was tested according to
Test Procedure II for 30 seconds for each marble square and 65 Next, the same marble tiles from Table 5 were polished
the 20° and 60° gloss was measured. These gloss values can for an additional 30 seconds and the gloss values were
be found in Table 2. remeasured. These gloss values can be found in Table 6.
 5,551,960
17 18
Example 1. A slurry was prepared by thoroughly mixing the
TABLE 6 abrasive particles and other ingredients. The resulting slurry
90SECOND GLOSS VALUES was forced with a spatula through a stainless steel screen that
FOR EXAMPLE 2 had circular openings that were approximately 2 mm in
diameter and onto the backing. The resulting material was
Marble type 20° 60° exposed to one Fusion Systems visible light which operated
green 48.8 68.8
at 240 Watts/cm. An exposure of about 3 meters/minute was
white 93.6 101.7 used. Next, the material was heated for about 20 minutes at
beige 72O 87.9 175o C.
black 76.8 90.1 10 For Example 6, the slurry consisted of 61.4 parts UAR,
4.2 parts PETA, 8.4 parts IBA, 8.4 parts ER, 0.8 part PH1, .
The gloss measurements were made on commercially 0.4 part PH2, 6 parts PEG, 0.3 part red pigment, 0.1 part I33
available marble tiles and these values can be found in Table wetting agent, 5 parts synthetic diamond that had average
7. The marble squares were purchased from Drake Marble particle size of 15 micrometers and 5 parts of ASF. For
Co., St. Paul, Minn. 15 Example 7, the slurry consisted of by weight 56.94 parts
UAR, 13.5 parts HDODA, 9 parts IBA, 9 parts ER, 0.8 part
TABLE 7 PH1, 0.4 part PH2, 6 parts PEG, 0.3 part red pigment, 0.1
GLOSS WALUES OF COMMERCIALLY
part I33 wetting agent, 5 parts synthetic diamond that had
AVAILABLE MARBLE TILES average particle size of 3 micrometers and 5 parts of ASF.
20 The abrasive articles were tested according to Test Pro
Marble type 20° 60° cedure I except that the marble disc was Negro Marquina
green 44.3 67.9 marble. The marble was first polished with Example 6 for
white T9.1 92.9 120 seconds, with gloss measurements taken prior to pol
beige
black
79.1
92.1 10.8
93.2 ishing and at 60 and 120 seconds. After polishing with the
25 abrasive article of Example 6, the marble was polished with
the abrasive article of Example 7. Gloss measurements were
EXAMPLES 3 THROUGH 5 taken after 30, 60,90 and 120 seconds of polishing. The test
results can be found in Table 9.
The abrasive articles for Examples 3 through 5 were made
in the same manner as Examples 1 and 2 except that different 30 TABLE 9
slurries were utilized. The slurry of Example 3 consisted of TEST PROCEUDRE
62.3 parts UAR, 4.2 parts PETA, 8.4 parts IBA, 8.4 parts
PEG, 0.84 part PH1, 5 parts synthetic diamond that had Example 6 Example 7
average particle size of 15 micrometers, 5 parts of WAO that Time 20° 60° 20° 60°
had average particle size of 15 micrometers, 4.7 parts of ASF 35
and 1.2 part CA1. The slurry of Example 4 consisted of 62.3 prior 0.4 5.0 26.6 519
parts EAR, 4.2 parts PETA, 8.4 parts IBA, 8.4 parts PEG, 30
60
kk
25.3
::::
51.0
81.4
90.6
91.9
97.6
0.84 part PH1, 5 parts synthetic diamond that had average 90 k: :ksk 92.6 99.1
particle size of 15 micrometers, 5 parts of WAO that had 20 26.6 51.9 94.2 100.0
average particle size of 15 micrometers, 4.7 parts of ASF and 40
1.2 part CA1. The slurry of Example 5 consisted of 53.3 **not measured
parts PAR, 12.1 parts PETA, 8.4 parts IBA, 8.4 parts PEG,
0.8 part PH1, 5 parts synthetic diamond that had average Comparative Example A
particle size of 15 micrometers, 5 parts of WAO that had Comparative Example A was a commercially available
average particle size of 15 micrometers, 5.8 parts of ASF and 45
abrasive disc from 3M sold under the trade designation "R30
1.2 part CA1. Flexible Diamond Discs' designed for polishing marble.
The abrasive articles were tested according to Test Pro This disc contained diamond abrasive particles that had an
cedure I and the results can be found in Table 8. The gloss average particle size of 15 micrometers dispersed in an
values were measured prior to polishing, and after 30, 60,90 50 epoxy binder devoid of addition polymerized resin, the
and 120 seconds of polishing. diamond and binder attached to a woven polyester backing
TABLE 8
which had a thermoplastic polyester presize.
A modified Test Procedure I was used in this set of
TEST PROCEDURE I examples to determine the life of the abrasive discs. The
55 head unit contained two flexible metal bond diamond discs
Example 3 Example 4 Example 5
commercially available from 3M under the trade designation
Time 20° 60° 20° 60° 20° 60° "M40”, two Example 1 abrasive discs and two Comparative
prior 1.2 5.4 10 3.9 1.0 4.3
Example A discs. The discs were alternated in the head unit.
30 6. 25.4 7.0 62.6 5.7 30.3 After every 30 seconds of polishing, the discs were checked
60 19.0 46.8 17.9 46.7 9.3 40.5 60 for wear. If a disc was worn, it was replaced with a new disc
90 22.7 52.2 20.8 51.2 12.3 47.0 of the same type. During testing the metal bond diamond
120 22.7 52.9 21.8 52.6 13.6 50.2 discs did not wear out. There were four Comparative
Example Aforevery Example 1 disc that was worn. Thus the
EXAMPLES 6 and 7
effective life of the Example 1 disc was approximately four
65 times that of Comparative Example A.
Examples 6 and 7 were made according to the following Various modifications and alterations of this invention
procedure. The backing for these examples was the same as will become apparent to those skilled in the art without
 5,551,960
19
departing from the scope and spirit of this invention, and it
should be understood that this invention is not to be unduly
limited to the illustrative embodiments set forth herein.
What is claimed is:
1. An abrasive article suitable for refining stone compris
ing a backing and a resilient composite comprising a binder
and abrasive particles, the abrasive particles adhered to the
backing to the binder, the binder comprising a cured resin,
said resin comprising unsaturated addition polymerizable
units and an effective amount of a plasticizer, the abrasive
particles being present in amount ranging from about 1 to
about 25 weight percent of the weight of binder and abrasive
particles, and the resilient composite having a Knoop hard
ness of greater than 1 and no more than 20.
2. An abrasive article in accordance with claim 1 wherein
the resin comprising addition polymerizable units comprises
monomers selected from the group consisting of acrylates,
acrylamides, and vinyl compounds.
3. An abrasive article in accordance with claim 1 wherein
the resin comprising addition polymerizable units includes
ionically initiated epoxy units.
4. An abrasive article in accordance with claim 1 wherein
the abrasive particles are present in the composite in an
amount ranging from about 3 to about 15 weight percent.
5. An abrasive article in accordance with claim 1 wherein
said backing comprises a woven backing having a first and
a second major surface, at least one of said first and second
major surfaces being substantially sealed with a thermoplas
tic resin presize coating, said composite adhered to said
presize coating.
6. An abrasive article in accordance with claim 5 wherein
said woven backing comprises polyester fibers.
7. An abrasive article in accordance with claim 6 wherein
said thermoplastic resin presize coating is a polyester resin.
8. An abrasive article in accordance with claim 1 wherein
said composite is comprised of a plurality of discrete nod
ules.
9. An abrasive article in accordance with claim 5 wherein
said composite comprised of a plurality of discrete nodules.
10. An abrasive article in accordance with claim 7
wherein said composite is comprised of a plurality of
discrete nodules.
11. An abrasive article in accordance with claim 1 wherein
said composite is comprised of a plurality of discrete areas
separated by channels.
12. An abrasive article in accordance with claim 1
wherein said plasticizer is selected from the group consisting
of polyvinyl chloride, cellulose esters, phthalate esters,
adipate esters, sebacate esters, tricresyl phosphate, polyols
and castor oil.
13. An abrasive article in accordance with claim 12
wherein said polyol is a polymer having polymerized eth
ylene glycol units.
14. An abrasive article in accordance with claim 13
wherein said polyol comprises polymerized ethylene glycol
units having a molecular weight ranging from about 200 to
about 1000.
15. An abrasive article in accordance with claim 1
wherein said composite has a Knoop hardness of at most 15
but at least 1. 60
16. An abrasive article in accordance with claim 7
wherein said composite has a Knoop hardness of at most 15
but at least 1.
20
17. An abrasive article suitable for refining stone com
prising an abrasive composite bonded to a backing wherein
the abrasive composite has a Knoop hardness less than 15
but at least 1, and wherein the abrasive composite com
5 prises:
a plurality of abrasive particles dispersed in a binder,
said binder comprising a cured resin and an effective
amount of a plasticizer, said resin comprising a plural
O ity of unsaturated addition polymerizable units.
18. An abrasive article according to claim 17 wherein the
abrasive composite Knoop hardness ranges from about 3 to
about 9.
19. An abrasive article according to claim 17 wherein the
15 resin is selected from the group consisting of acrylated
urethanes, acrylated epoxies, acrylated polyesters, ethyleni
cally unsaturated compounds, aminoplast derivatives having
pendant unsaturated carbonyl groups, isocyanurate deriva
tives having at least one pendant acrylate group, isocyanate
20 derivatives having at least one pendant acrylate group and
combinations thereof.
20. An abrasive article according to claim 17 wherein the
abrasive composite further comprises a plasticizer.
21. An abrasive article according to claim 20 wherein the
25
plasticizer is a polyol derivative.
22. An abrasive article according to claim 17 wherein the
abrasive composite has a patterned surface.
23. An abrasive article comprising an abrasive composite
30 bonded to a backing wherein the abrasive composite com
prises
a plurality of abrasive particles dispersed in a binder,
said binder comprising a cured resin, said resin compris
ing a plurality of unsaturated addition polymerizable
35 units and
a polyol derivative plasticizer dispersed in said binder, the
abrasive composition having Knoop hardness of
greater than 1 and no more than 20.
40 24. An abrasive article according to claim 23 wherein the
polyol derivative plasticizer is polyethyleneglycol.
25. An abrasive article according to claim 23 wherein the
abrasive composite has a patterned surface.
26. An abrasive article comprising:
45 a flexible backing and
a resilient composite, said composite comprising
from about 1 to about 25 wt-% abrasive particles, a
resilient binder, and
from about 1 to about 20 wt-% of a plasticizer, the
50 abrasive particles adhered to the flexible backing by
the resilient binder, the binder comprising a cured
resin, said resin comprising units polymerizable by a
free radical mechanism, and the resilient composite
having a Knoop hardness of greater than 1 and no
55 more than 20.
27. An abrasive article in accordance with claim 26
wherein said composite is comprised of a plurality of
discrete nodules.
28. An abrasive article in accordance with claim 26
wherein said composite is comprised of a plurality of
discrete areas separated by channels.
:: *k 3 k k